CN107033923A - Benzophenanthrene dodecyl bridge connects the synthetic method of perylene tetramethyl acid butyl ester binary compound discotic mesogenic material - Google Patents
Benzophenanthrene dodecyl bridge connects the synthetic method of perylene tetramethyl acid butyl ester binary compound discotic mesogenic material Download PDFInfo
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Abstract
The invention discloses the synthetic method that a kind of benzophenanthrene dodecyl bridge connects perylene tetramethyl acid butyl ester binary compound discotic mesogenic material.Synthetic route is divided into three below part：Part I first closes into perylene tetramethyl acid butyl ester, then closes into perylene list acid anhydride diformazan acid butyl ester；Part II first synthesizes the hexyloxy benzophenanthrene of monohydroxy five, then synthesizes the alkoxy benzophenanthrene with a ω bromine side chain；The intermediate synthesis benzophenanthrene dodecyl bridge that Part III obtains above-mentioned two parts connects perylene tetramethyl acid butyl ester binary compound.Triphenylene possesses good optical property and heat endurance, and the raw material of the such compound of synthesis is easy to get, and product is easy to purification；Er perylene derivative molecules are because of its big conjugated system, it is easy to carry out structural modification, and show excellent photoelectric property.The present invention, which connects triphenylene and perylene derivative by flexible bridge chain, to be formed benzophenanthrene dodecyl bridge and connects perylene tetramethyl acid butyl ester binary compound discotic mesogenic material.The material can be applied in the photoelectric devices such as organic photovoltaic material, liquid crystal material.
Description
Technical field
Connect perylene tetramethyl acid butyl ester binary compound discotic mesogenic material the present invention relates to a kind of benzophenanthrene dodecyl bridge
Synthetic method.
Background technology
Chandrasekhar synthesized equal six benester compound in 1977 and is found that the property of its discotic mesogenic first
Matter, discotic liquid-crystalline molecules are made up of the polycyclic aromatic proton of conjugation with big pi bond and three to eight, core periphery flexible side-chains mostly.
The discotic liquid-crystalline molecules nuclear unit for being reported out has phenyl ring nucleoid, benzophenanthrene nucleoid, phthalocyanine nucleoid, porphyrin core and perylene class
Core.
Benzophenanthrene and its derivative are the class materials with π-pi-electron conjugated structure, and this kind of material possesses good liquid
Brilliant property, can be stacked into columnar phase so that electric charge can be transmitted in one-dimensional passage, Benzophenanthrene under π-π active forces
Compound has good optical property and heat endurance, and the raw material of the such compound of synthesis is easy to get, and product is easy to purification, because
This Benzophenanthrene compound for being rich in flexible alkyloxy side chain can be used as electron donor unit.Perylene analog derivative has excellent
Photoelectric property, while being also good electron acceptor unit, its synthetic method is ripe, possesses liquid crystal property.
, will in the present invention using triphenylene as electron donor unit , perylene derivatives as electron acceptor unit
Electron donor unit and electron acceptor unit are connected by flexible bridge chain, form the property with photoinduction cyclic voltammetry method
Discotic mesogenic binary compound.Such compound future can be applied in organic photovoltaic material such as solar cell, liquid crystal material
Expect in equimolecular device.
The content of the invention
Connect perylene tetramethyl acid butyl ester binary compound plate-like liquid it is an object of the invention to provide a kind of benzophenanthrene dodecyl bridge
The synthetic method of brilliant material.
Synthetic route of the present invention is divided into three below part：Part I Xian is using perylene tetracarboxylic acid dianhydride, potassium hydroxide as original
Material closes into perylene tetramethyl acid butyl ester, should instead give birth into perylene list acid anhydride dibutyl ester；Part II under the oxidation of ferric trichloride it is adjacent oneself
The coupling reaction generation hexyloxy benzophenanthrene of monohydroxy-five occurs for epoxide phenol and adjacent two hexyloxies benzene, then with the own oxygen of monohydroxy-five
Base benzophenanthrene and the alkoxy benzophenanthrene that 1,12- dibromo-dodecanes are that Material synthesis has a ω-bromine side chain；Part III will
The perylene binary compound of intermediate synthesis of alkyl bridging benzophenanthrene-that above-mentioned two parts are obtained.
Benzophenanthrene and its derivative possess good liquid crystal property, with the electric charge transmission and energy transfer in one-dimensional square
Performance, and synthesis Benzophenanthrene compound raw material be easy to get, product be easy to purification；Perylene derivative has big conjugated system to Er,
It is also good electron acceptor simultaneously, its synthetic method is ripe, possesses liquid crystal property.In the present invention by triphenylene
As electron donor unit , perylene derivatives as electron acceptor unit, they are connected by flexible bridge chain, being formed has photo-induction
Lead the discotic mesogenic binary compound of the property of cyclic voltammetry method.Such compound future can be applied in organic photovoltaic material
In material, liquid crystal material equimolecular device.
Brief description of the drawings
Fig. 1 is the structure that benzophenanthrene dodecyl bridge of the present invention connects perylene tetramethyl acid butyl ester binary compound discotic mesogenic material
Formula.
Fig. 2 is the chemical equation of synthetic route of the present invention.
Embodiment
Embodiment：
Chemical reagent and solvent used in embodiment are that analysis is pure.
(1) synthesis of perylene tetramethyl acid butyl ester (compound 1)：
10.52 grams of potassium hydroxide and 400 milliliters of water are taken to load reactor, stirring dissolves it.3.80 grams of Weigh Compound
Perylene tetracarboxylic acid dianhydride is poured into potassium hydroxide solution, is warming up to 70 DEG C of condensing refluxes 1.5 hours.Rear question response liquid has been reacted to be down to
Room temperature, suction filtration collects filtrate stand-by.Adjust the pH to 9 of filtrate；13.90 grams of 1- bromination of n-butane and 3.90 grams are added thereto
Methyl tricapryl ammonium chloride, is warming up to 2 hours of 100 DEG C of condensation cycle stirring reactions.Reaction generation glassy yellow milk, is poured out
Reaction water, 50 milliliters of absolute ethyl alcohols are added into glassy yellow milk, there is yellow mercury oxide precipitation, suction filtration, with 20 milliliters of anhydrous second
Alcohol washs filter cake in two times.Obtain 1,6.20 grams of yellow solids of compound, yield 98.24%.Mp:162.6-163.8℃.IR
(KBr)νmax(cm-1):3430,2930,2850,1730,1630,1460,1400,1270,1170,1000,747.
(2) synthesis of perylene list acid anhydride diformazan acid butyl ester (compound 2)：
Taking 4.00 g of compound, 1,18 milliliters of toluene and normal heptane mixed liquor, (toluene is 1 with normal heptane volume ratio:5) add
Reactor, is warming up to 80 DEG C of stirrings and promotes compound 1 to dissolve in 30 minutes, add 1.17 grams of p-methyl benzenesulfonic acid, be warming up to 95 DEG C
Condensing reflux stirring reaction 7 hours.Question response liquid temperature degree is down to room temperature, and suction filtration, collection filter cake is red solid crude product, takes thick
Product is further purified using the method for recrystallization.The dichloromethane dissolving crude product of monoploid product, is added dropwise the first of two volumes
Alcohol separates out solid, in triplicate, obtains 2,2.90 grams of red solids of compound, yield 90.63%.Mp:200 DEG C of .IR (KBr) of ＞
νmax(cm-1):3430,2920,2850,1730,1630,1770,1700,1590,1510,1470,1290,1150,1130,
1010,857,805,737.
(3) synthesis of adjacent hexyloxy-phenol (compound 3)：
Take 30 grams of catechols, 45 grams of 1- bromos n-hexanes, 60 grams of Anhydrous potassium carbonates, 2.28 grams of KIs and 300 milliliters
Absolute ethyl alcohol, 85 DEG C of condensing refluxes react 12 hours, are cooled to suction filtration after room temperature, and filtrate decompression revolving removes solvent, 0.5mmHg
Vacuum distillation in the case of collect 84 DEG C of cut, obtain 3,15.46 grams of colourless oil liquids of compound, yield 29.52%.Bp:
106±3℃.IR(KBr)νmax(cm-1):1260,930.1H NMR(300MHz,CDCl3)δ:6.95-6.82(m,4H),
5.68 (s, 1H), 4.02 (t, J=6.6Hz, 2H), 1.83-1.76 (m, 2H), 1.48-1.31 (m, 6H), 0.91 (t, J=
6.9Hz,3H).
(4) synthesis of adjacent two hexyloxy-phenol (compound 4)：
Take 10 grams of catechols, 45 grams of 1- bromos n-hexanes, 37.26 grams of Anhydrous potassium carbonates, 3.32 grams of KIs and 125 millis
Absolute ethyl alcohol is risen, 85 DEG C of condensing refluxes react 60 hours, is cooled to suction filtration after room temperature, filtrate decompression revolving removes solvent,
The cut of 142 DEG C of collection, obtains compound 4,24.53 grams of colourless oil liquids, yield in the case of 0.5mmHg vacuum distillation
96.96%.Bp:255±3℃.IR(KBr)νmax(cm-1):1250,939.1H NMR(300MHz,CDCl3)δ:6.89(s,
4H), (t, J=6.9Hz, the 6H) of 3.99 (t, J=6.9Hz, 4H), 1.83-1.76 (m, 4H), 1.49-1.31 (m, 12H), 0.90
(5) synthesis of the hexyloxy of monohydroxy-five benzophenanthrene (compound 5)：
Take 1.16 g of compound 3 and 3.32 g of compound 4 to be dissolved in 60 milliliters of dichloromethane, be added dropwise through constant pressure funnel
Into 80 milliliters of dichloromethane solutions containing 12.96 grams of anhydrous ferric trichlorides and 8 milliliters of nitromethanes, be added dropwise 30 minutes it is complete
Finish, after control reacting liquid temperature reacts 4 hours between 0~3 DEG C, add 30 ml methanols and 60 milliliters of water terminating reactions, point
Go out organic layer, with 30 milliliters of dichloromethane aqueous layer extracteds three times, collect all organic layers, then with 20 milliliters of saturated common salt water washings
Organic layer, separates organic layer, adds after anhydrous sodium sulfate drying water removal, vacuum rotary steam removes solvent, obtained crude product is used
200-300 mesh silica gel column chromatography purifies (leacheate：Petrol ether/ethyl acetate, volume ratio 50:1) 5,1.80 grams of compound, is obtained
White solid, yield 40.45%.Mp:47.7-50.1℃.IR(KBr)νmax(cm-1):3040,1240,837.1H NMR
(400MHz,CDCl3)δ:7.96(s,1H),7.83(s,3H),7.82(s,1H),7.77(s,1H),5.91(s,1H),4.31-
4.19(m,10H),1.98-1.90(m,10H),1.59-1.40(m,30H), 0.96-0.92(m,15H)
(6) synthesis of the hexyloxy benzophenanthrene (compound 6) of 12 epoxide of bromo-five：
Take 1.19 g of compound, 5,3.15 grams of 1,12- dibromo-dodecanes, 0.15 gram of TBAB, 0.36 gram of hydroxide
After reaction being stirred at room temperature under potassium, 14 milliliters of water and 22 milliliters of dichloromethane, nitrogen atmosphere 24 hours, organic layer is separated, with 20 millis
Rise dichloromethane aqueous layer extracted three times, collect all organic layers, then with 15 milliliters of saturated common salt water washing organic layers, separate organic
Layer, is added after anhydrous sodium sulfate drying water removal, vacuum rotary steam removes solvent, obtained crude product 200-300 mesh silica gel column layers
Analysis purification (leacheate：Petrol ether/ethyl acetate, volume ratio 100:1) compound 6,1.20 grams of Off-white solids, yield, are obtained
75.6%.IR(KBr)νmax(cm-1):3430,2930 (C-H), 2850,1620 (C=C), 1520,1440,1390,1260
(C-O-C),1170,1050,925,836(C-X).1H NMR(400MHz,CDCl3)δ:7.84 (s, 6H), 4.23 (t, J=
6.5Hz, 12H), 3.40 (t, J=6.9Hz, 2H), 1.98-1.83 (m, 12H), 1.67-1.50 (m, 16H), 1.42-1.29 (m,
32H), 0.93 (t, J=7.0Hz, 15H)
(7) synthesis of the hexyloxy benzophenanthrene (compound 7) of 12 epoxide of iodo-five：
0.50 g of compound 6 is taken to be taken out with oil pump 30 minutes, under nitrogen protection, 0.91 gram of KI of addition, 20 milliliters of acetone,
60 DEG C of condensing refluxes are warming up to react 24 hours.Compound 7 is generated in reaction solution, without processing, next step reaction is directly entered.
(8) five hexyloxy benzophenanthrene dodecyl bridges connect the synthesis of perylene tetramethyl acid butyl ester (compound 8)：
0.28 g of compound, 2,10 milliliters of n-butanols, 1.10 grams of Carbon Dioxides are added into the reaction solution of generation compound 7
Potassium.50 DEG C are cooled the temperature to, the lower condensing reflux of nitrogen protection reacts 48 hours.Question response liquid temperature degree is down to room temperature, to reaction solution
In plus 200 milliliters of water, add 30 milliliters of ethyl acetate, ethyl acetate liquid collected after extraction, water layer is with 30 milliliters of acetic acid second
Ester is extracted in three times, merges all organic layers, with 15 milliliters of saturated common salt water washing organic layers.The anhydrous sulphur of obtained organic liquor
Sour sodium is dried, and crocus solid crude product is obtained after vacuum rotary steam, crude product purified by silica gel post is further purified into (leacheate：Oil
Ether/methylene chloride volume compares 1：3).Obtain compound 8, crocus solid 0.24g, yield 31.87%.IR(KBr)νmax(cm-
1):2930 (C-H), 2850,2360,1720 (C=O), 1620,1510 (C=C), 1430,1380,1270 (C-O-C), 1170,
838.1H NMR(500MHz,CDCl3)δ:8.24 (d, J=8.0Hz, 4H), 8.00 (d, J=8.0Hz, 4H), 7.84 (s, 6H),
4.35 (t, J=6.5Hz, 8H), 4.24 (t, J=6.5Hz, 12H), 1.96-1.92 (m, 12H), 1.81-1.78 (m, 8H),
1.60–1.34(m,52H),1.01–0.94(m,24H).MS(ESI):C96H130O14Na for[M+Na]+,calculated
1530.9392,found 1530.0000.Elemental analysis calcd for C96H130O14(1508):C,
76.46,H,8.69,Found:C,75.77,H,8.68,N,<0.30。
Claims (1)
1. a kind of benzophenanthrene dodecyl bridge connects the synthetic method of perylene tetramethyl acid butyl ester binary compound discotic mesogenic material, it is special
Levy and be to concretely comprise the following steps：
(1) synthesis of perylene tetramethyl acid butyl ester (compound 1)：
10.52 grams of potassium hydroxide and 400 milliliters of water are taken to load reactor, stirring dissolves it.The Ke perylenes four of Weigh Compound 3.80
Formic acid dianhydride is poured into potassium hydroxide solution, is warming up to 70 DEG C of condensing refluxes 1.5 hours.React rear question response liquid and be down to room
Temperature, suction filtration collects filtrate stand-by.Adjust the pH to 9 of filtrate；13.90 grams of 1- bromination of n-butane and 3.90 grams of first are added thereto
Base trioctylmethylammonium chloride, is warming up to 2 hours of 100 DEG C of condensation cycle stirring reactions.Reaction generation glassy yellow milk, is poured out anti-
Ying Shui, 50 milliliters of absolute ethyl alcohols are added into glassy yellow milk, there is yellow mercury oxide precipitation, suction filtration, with 20 milliliters of absolute ethyl alcohols
Filter cake is washed in two times.Obtain 1,6.20 grams of yellow solids of compound, yield 98.24%.Mp:162.6-163.8℃.IR
(KBr)νmax(cm-1):3430,2930,2850,1730,1630,1460,1400,1270,1170,1000,747.
(2) synthesis of perylene list acid anhydride diformazan acid butyl ester (compound 2)：
Taking 4.00 g of compound, 1,18 milliliters of toluene and normal heptane mixed liquor, (toluene is 1 with normal heptane volume ratio:5) reaction is added
Device, is warming up to 80 DEG C of stirrings and promotes compound 1 to dissolve in 30 minutes, add 1.17 grams of p-methyl benzenesulfonic acid, be warming up to 95 DEG C of condensations
Return stirring reacts 7 hours.Question response liquid temperature degree is down to room temperature, and suction filtration, collection filter cake is red solid crude product, takes crude product
Further purified using the method for recrystallization.The dichloromethane dissolving crude product of monoploid product, is added dropwise the methanol analysis of two volumes
Go out solid, in triplicate, obtain 2,2.90 grams of red solids of compound, yield 90.63%.Mp:200 DEG C of .IR (KBr) ν of ＞max
(cm-1):3430,2920,2850,1730,1630,1770,1700,1590,1510,1470,1290,1150,1130,1010,
857,805,737.
(3) synthesis of adjacent hexyloxy-phenol (compound 3)：
Take 30 grams of catechols, 45 grams of 1- bromos n-hexanes, 60 grams of Anhydrous potassium carbonates, 2.28 grams of KIs and 300 milliliters anhydrous
Ethanol, 85 DEG C of condensing refluxes react 12 hours, are cooled to suction filtration after room temperature, and filtrate decompression revolving removes solvent, and 0.5mmHg's subtracts
The cut of 84 DEG C of collection, obtains 3,15.46 grams of colourless oil liquids of compound, yield 29.52% in the case of pressure distillation.Bp:106±
3℃.IR(KBr)νmax(cm-1):1260,930.1H NMR(300MHz,CDCl3)δ:6.95-6.82(m,4H),5.68(s,
1H), (t, J=6.9Hz, the 3H) of 4.02 (t, J=6.6Hz, 2H), 1.83-1.76 (m, 2H), 1.48-1.31 (m, 6H), 0.91
(4) synthesis of adjacent two hexyloxy-phenol (compound 4)：
Take 10 grams of catechols, 45 grams of 1- bromos n-hexanes, 37.26 grams of Anhydrous potassium carbonates, 3.32 grams of KIs and 125 milliliters of nothings
Water-ethanol, 85 DEG C of condensing refluxes react 60 hours, are cooled to suction filtration after room temperature, and filtrate decompression revolving removes solvent, 0.5mmHg's
The cut of 142 DEG C of collection, obtains 4,24.53 grams of colourless oil liquids of compound, yield 96.96% in the case of vacuum distillation.Bp:
255±3℃.IR(KBr)νmax(cm-1):1250,939.1H NMR(300MHz,CDCl3)δ:6.89 (s, 4H), 3.99 (t, J=
6.9Hz, 4H), 1.83-1.76 (m, 4H), 1.49-1.31 (m, 12H), 0.90 (t, J=6.9Hz, 6H)
(5) synthesis of the hexyloxy of monohydroxy-five benzophenanthrene (compound 5)：
Take 1.16 g of compound 3 and 3.32 g of compound 4 to be dissolved in 60 milliliters of dichloromethane, 80 are added dropwise to through constant pressure funnel
In dichloromethane solution of the milliliter containing 12.96 grams of anhydrous ferric trichlorides and 8 milliliters of nitromethanes, dropwise addition is finished for 30 minutes, is controlled
After reacting liquid temperature processed reacts 4 hours between 0~3 DEG C, 30 ml methanols and 60 milliliters of water terminating reactions are added, are separated organic
Layer, with 30 milliliters of dichloromethane aqueous layer extracteds three times, collects all organic layers, then organic with 20 milliliters of saturated common salt water washings
Layer, separates organic layer, adds after anhydrous sodium sulfate drying water removal, vacuum rotary steam removes solvent, obtained crude product 200-300
Mesh silica gel column chromatography purifies (leacheate：Petrol ether/ethyl acetate, volume ratio 50:1) 5,1.80 grams of whites of compound, are obtained to consolidate
Body, yield 40.45%.Mp:47.7-50.1℃.IR(KBr)νmax(cm-1):3040,1240,837.1H NMR(400MHz,
CDCl3)δ:7.96(s,1H),7.83(s,3H),7.82(s,1H),7.77(s,1H),5.91(s,1H),4.31-4.19(m,
10H),1.98-1.90(m,10H),1.59-1.40(m,30H),0.96-0.92(m,15H)
(6) synthesis of the hexyloxy benzophenanthrene (compound 6) of 12 epoxide of bromo-five：
Take 1.19 g of compound, 5,3.15 grams of 1,12- dibromo-dodecanes, 0.15 gram of TBAB, 0.36 gram of potassium hydroxide,
After reaction being stirred at room temperature under 14 milliliters of water and 22 milliliters of dichloromethane, nitrogen atmosphere 24 hours, organic layer is separated, with 20 milliliter two
Chloromethanes aqueous layer extracted three times, collects all organic layers, then with 15 milliliters of saturated common salt water washing organic layers, separates organic layer,
Add after anhydrous sodium sulfate drying water removal, vacuum rotary steam removes solvent, obtained crude product is carried with 200-300 mesh silica gel column chromatographies
Pure (leacheate：Petrol ether/ethyl acetate, volume ratio 100:1) compound 6,1.20 grams of Off-white solids, yield, are obtained
75.6%.IR(KBr)νmax(cm-1):3430,2930 (C-H), 2850,1620 (C=C), 1520,1440,1390,1260
(C-O-C),1170,1050,925,836(C-X).1H NMR(400MHz,CDCl3)δ:7.84 (s, 6H), 4.23 (t, J=
6.5Hz, 12H), 3.40 (t, J=6.9Hz, 2H), 1.98-1.83 (m, 12H), 1.67-1.50 (m, 16H), 1.42-1.29 (m,
32H), 0.93 (t, J=7.0Hz, 15H)
(7) synthesis of the hexyloxy benzophenanthrene (compound 7) of 12 epoxide of iodo-five：
Take 0.50 g of compound 6 to be taken out with oil pump 30 minutes, under nitrogen protection, add 0.91 gram of KI, 20 milliliters of acetone, heating
Reacted 24 hours to 60 DEG C of condensing refluxes.Compound 7 is generated in reaction solution, without processing, next step reaction is directly entered.
(8) five hexyloxy benzophenanthrene dodecyl bridges connect the synthesis of perylene tetramethyl acid butyl ester (compound 8)：
0.28 g of compound, 2,10 milliliters of n-butanols, 1.10 grams of Anhydrous potassium carbonates are added into the reaction solution of generation compound 7.Will
Temperature is down to 50 DEG C, and the lower condensing reflux of nitrogen protection reacts 48 hours.Question response liquid temperature degree is down to room temperature, adds into reaction solution
200 milliliters of water, add 30 milliliters of ethyl acetate, and ethyl acetate liquid, water layer 30 milliliters of ethyl acetate point are collected after extraction
Three extractions, merge all organic layers, with 15 milliliters of saturated common salt water washing organic layers.Obtained organic liquor anhydrous sodium sulfate
Dry, crocus solid crude product is obtained after vacuum rotary steam, crude product purified by silica gel post is further purified into (leacheate：Petroleum ether/bis-
Chloromethanes volume ratio 1：3).Obtain compound 8, crocus solid 0.24g, yield 31.87%.IR(KBr)νmax(cm-1):
2930 (C-H), 2850,2360,1720 (C=O), 1620,1510 (C=C), 1430,1380,1270 (C-O-C), 1170,
838.1H NMR(500MHz,CDCl3)δ:8.24 (d, J=8.0Hz, 4H), 8.00 (d, J=8.0Hz, 4H), 7.84 (s, 6H),
4.35 (t, J=6.5Hz, 8H), 4.24 (t, J=6.5Hz, 12H), 1.96-1.92 (m, 12H), 1.81-1.78 (m, 8H),
1.60–1.34(m,52H),1.01–0.94(m,24H).MS(ESI):C96H130O14Na for[M+Na]+,calculated
1530.9392,found 1530.0000.Elemental analysis calcd for C96H130O14(1508):C,
76.46,H,8.69,Found:C,75.77,H,8.68,N,<0.30.
The chemical reagent and solvent are that analysis is pure.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461628A (en) * | 2014-07-07 | 2016-04-06 | 江苏和成新材料有限公司 | Triphenylene-perylene monoimide diformate binary compound, preparation method and applications thereof |
| CN105541616A (en) * | 2015-12-05 | 2016-05-04 | 桂林理工大学 | Hexaalkoxytriphenylene-flexible bridge-perylenetetracarboxylic acid tetraester binary compound and preparation method thereof |
| CN106047369A (en) * | 2016-06-27 | 2016-10-26 | 桂林理工大学 | Synthesis method of benzophenanthrene hexaalkoxyl bridged dodecoxyl phenyl porphyrin binary compound disc-shaped liquid crystal material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461628A (en) * | 2014-07-07 | 2016-04-06 | 江苏和成新材料有限公司 | Triphenylene-perylene monoimide diformate binary compound, preparation method and applications thereof |
| CN105541616A (en) * | 2015-12-05 | 2016-05-04 | 桂林理工大学 | Hexaalkoxytriphenylene-flexible bridge-perylenetetracarboxylic acid tetraester binary compound and preparation method thereof |
| CN106047369A (en) * | 2016-06-27 | 2016-10-26 | 桂林理工大学 | Synthesis method of benzophenanthrene hexaalkoxyl bridged dodecoxyl phenyl porphyrin binary compound disc-shaped liquid crystal material |
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